Supported sodium catalyst and preparation thereof



Patented Dec. 14, 1948 SUPPORTED? SODIUM CATALYSTHAND PREPARATION" THEREOF Georgie Alexander -Mills, Swarthn'lore,v .Pa ass-w signon. to- Houdr-y Process Corporation; Wile mingtongfiel a corporation of Delaware No Drawing. Application February 6,1947, Serial No. 726,957

6, Claims. 1

The: present: invention relates to improved preparations and contact masses for use in reactions' -JIBQHiIing: metallic sodium. More particularly the invention is concerned with improved methodszforithe ready formation of metallic surfaces of sodiumimcleamhighly active form.

Metallicdsodium'lisknown in-theart as a catalyst imhydrocarbon:polymerization reactions such as in'xthewmass polymerization vof conjugated, diolefins particularlyfor the production of synthetic rubber; Imsuch-vprocesses the characteristics of the sodiumacontact surfaceis-of utmost importance in: determining the. course and efficiency of the reaction-.1 The sodiuml'm'etalbeing insolid form and extremely active, readily picks up impurities, such as: oxygen,, even when present in smallest amounts, thus-impairing the-catalytic activity of the surface'xor otherwise interfering1 with the. desired polymerization: reaction;

In theconventional practice of preparingmetallic"sodium\ contact masses, iron combs or rods are-dipped: into: 4 amolten sodium bath, thereafter withdrawn and. coated withparafiin. The thuscoated'combs or.rods. are then: transferred to the reaction vessel in which the polymerization of thexunsaturated: hydrocarbon .is' to be carried out. Theeparafiin coating protects-.the sodium surface-against: deterioration; :as byoxidation, and to expose-the sodiumasurfacepforxuse in the reactor it isxnec'essary torem'ovewthe protective covering in an atmosphere of inert or reducing gas. In the use-ofthisinvolve'd' technique, considerable care must be exercised in the preparation of the contact surface and even then extreme difllculty has been experienced in obtaining good results.

I have discovered that metallic sodium surfaces of controllable thickness, in highly active state and free from deleterious contaminants can be readily prepared by a comparatively simple pro" cedure of depositing the sodium on a non-porous surface from a solution of the metallic sodium in liquid ammonia. In accordance with the invention, the deposition of the sodium on the supporting surface can be effected directly in the vessel in which a desired chemical reaction, such as polymerization, is to be subsequently carried out, thereby further reducing the possibility of contamination.

In accordance with a preferred embodiment a non-porous supporting mass presenting an extenslve surface area, such as glass Wool, is provided in a closed reaction vessel. The solution of sodium in liquid ammonia is introduced into the vessel and permitted to coat the walls of the 2 vessel as well' as thesupporting'massr The'am monia is then permitted to evap'orate'and'with} drawn from the vessel, precaution-beingtakento avoid introduction into the vessel of air-"criticis ture. The thickness of the"sodium"'deposit"can be controlled by selecting the required concentration of sodium in the ammoni'asolution;

Any inert non-porous surface canelbeszemployed on which to deposit: the metallic :sodium,...which surface may be provided: byithe; interi'onwalls of the reaction vessel itself; however, in order to ob:- tain a maximum contact surface it is preferred to cemploylmaterials.v oifering,, a more extensive surface, suchas none-porous, non-reactive fibrous, filamentous or finely granularmateri'al's (geneerallyvbelow- ZOOmesh and preferably not above about. 50 micronsize). In reactionswhereinzthe more highly extended surface area. providedflb'y these materials is not required, the deposit" of sodium on the walls of the reaction vessel alone may suffice or may be supplementedby the inclusion of rods, Wires or pellets of suitable material for deposition of sodiumthereon. The-surfacev to be coated may be lofnanylxnomporous material which does not react -withz,sodium. or the ammonia solution, such as: glass; glazed 'oorcelain; quartz sand orlmetal.

The contactv surfaces of. metallic sodium as above prepared; can be advantageously employed in known reactions for polymerization .of. comjugateddiolefins orother unsaturated-hydrocarbons employing metallic .sodiumrcatalyst such as in the mass polymerization of isoprene or butadiene. By controlling the conditions ineluding the temperature, rate, and extent of polymerization, various polymerization products can be obtained ranging from more or less viscous drying oils through tacky semi-solids to solid rubberl-ike materals.

Example I ing and vessel walls, the ammonia was evaporated leaving a thin uniform coating of metallic sodium on all the exposed surface within the tube The hydrocarbon charge stock was a blend of 170 to 175 F. water through a jacket surrounding the reaction tube.

The product was combined in several cuts, of which out No. 4, representing operation from 220 minutes to 265 minutes, was-fairly representative. An A. S. T. M. distillation was as follows:

Degrees F. Int 101 90, 95, Resin residues after 88% dist.

Approximately 35%of unsaturates in the original charge stock were polymerized to heavy oil which had'the. characteristic nature of a drying oil. 1 Example II Another run with freshly prepared sodium catalyst was made in thesame vessel with the same charge and conditions except that the temperatures were about180 to 190 F. with run time of 288 minutes. The percent of unsaturates reacting was 74.%. The reaction product was a heavy drying oil which dried to a hard smooth lacquer-like fiinish.

Example III Another run was made similar to that in the first example except that the rate of charge was approximately 4.0 00. per minute and the duration of the run-was 368 minutes. Reaction of the unsaturates during thefirst hour was about during the secondhour about 10%, during the third hour about 5%, during the fourth hour about 3.5%. Maximum conversion during this run was 19.5%. The product was a less viscous drying 'oil than obtained in the preceding example.

Metallic sodium has other well known uses in addition to that of a catalyst. For instance it has been employed in some chemical reactions as a reducing agent, and also as a reactant in organic syntheses, for example in reactions with organic halides as in the classical Fittig and Wurtz syritheses] The provision of metallic sodium surfaces free from interfering contaminants may also be found advantageous in connections with these reactions Obviously many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim as my invention:

1. The process of preparing active surfaces of substantially pure metallic sodium which comprises treating an inert non-porous material with a solution of sodium in liquid ammonia; andevap orating the ammonia, while preventing accessof air and moisture to the treated material during evaporation. y

2. The process of claim 1 in which saidinert non-porous material is glass wool;- .:.I

3. The method of preparing metallic sodium surfaces for use in catalytic reactions which comprises providing an inert non-porous supporting mass of extensive surface area in a closed reactor, depositing a film of metallic sodium on said sup porting mass by contacting'said supporting ma's's while in said reactor with a solutionof sodium in liquid ammonia, and withdrawing vaporized ammonia from said reactor while preventing access of air and moisture into said reac'tor.

4. The process of claim 3 in which saidsup= porting mass consists of a packingof glass'wool'.

5. The process of preparing a supported cata- 40 lyst which comprises treating an inert non-porous supporting mass of extensive surface area with a solution of sodium in liquid ammoniaand evap orating the ammonia, while preventing access'of air and moisture to the treated material 'during evaporation.

6. A supported catalyst consisting essentially of glass Wool having thereon an active film of sub stantially pure metallic sodium in the form de o posited from solution in liquid ammonia. f

GEORGE ALEXANDER; MILLS;-'

No references cited. 

